Solidifying Agent for Fibrous Treatment Object and Method of Fixing Treatment Therefor

ABSTRACT

An object of the invention is to provide a solidifying agent for fibrous treatment objects to be treated or a method of fixing treatment for fibrous treatment objects to be treated. According to the present invention, the solidifying agent for the fibrous treatment objects to be treated mainly contains an aqueous sulfide solution, in which one or a mixture of Group 1 or Group 2 metals or other alkali metal substances is ionically bonded with sulfur. Further, according to the present invention, the solidifying agent for the fibrous treatment objects to be treated mainly contains an aqueous solution of polysulfide of one or a mixture of Group 1 or Group 2 metals or other alkali metal substances.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a solidifying agent for fibroustreatment objects to be treated and a method of fixing treatment forfibrous treatment objects to be treated.

BACKGROUND TECHNOLOGY

Fibrous asbestos and metals have been used as building materials.Especially, due to superior characteristics such as durability, heatresistance, chemical resistance, and electrical insulation, and also lowcost, asbestos have been widely used for various applications.

When fibrous substances used in building materials scatter and areinhaled in a human body, the fibrous substances may be harmful to thehuman body. Accordingly, measures have been taken to prohibit usethereof.

However, the fibrous substances have been already heavily used inbuilding materials. Therefore, in addition to the prohibition of futureuse thereof, it is necessary to prevent the existing fibrous substancesfrom scattering, and to provide a technology for hardening the existingfibrous substances.

The technology of hardening the fibrous substances is necessary not onlyfor continuous use of the existing fibers, but also for preventing thefibrous substances from scattering when the existing fibrous substancesare removed.

DISCLOSURE OF THE INVENTION

In view of the problems described above, according to a first aspect ofthe present invention, a solidifying agent for fibrous treatment objectsto be treated contains an aqueous sulfide solution, in which one or amixture of Group 1 or Group 2 metals or other alkali metal substances isionically bonded with sulfur.

According to a second aspect of the present invention, a solidifyingagent for fibrous treatment objects to be treated contains an aqueoussolution of polysulfide of one or a mixture of Group 1 or Group 2 metalsor other alkali metal substances.

According to a third aspect of the present invention, the solidifyingagent for fibrous treatment objects to be treated in the first or secondaspect contains an aqueous solution of metal hydroxide or an aqueoussolution containing fine particles of metal hydroxide.

According to a fourth aspect of the present invention, a method offixing treatment for fibrous treatment objects to be treated includes astep of coating the fibrous treatment objects with the solidifying agentin the first or second aspect, or soaking the solidifying agent in thefirst or second aspect in the fibrous treatment objects, so that thefibrous treatment objects to be treated are hardened.

According to a fifth aspect of the present invention, in the method offixing treatment for the fibrous treatment objects to be treated in thefourth aspect, after adding a surfactant to the solidifying agent in thefirst or second aspect, the solidifying agent in the first or secondaspect coats or soaks in the fibrous treatment objects to be treated.

According to a sixth aspect of the present invention, in the method offixing treatment for the fibrous treatment objects to be treated in thefourth or fifth aspect, after adding water to the solidifying agent inthe first or second aspect to adjust a specific gravity thereof, thesolidifying agent in the first or second aspect coats or soaks in thefibrous treatment objects to be treated.

According to a seventh aspect of the present invention, in the method offixing treatment for the fibrous treatment objects to be treated in oneof the fourth to sixth aspects, after or while adding an aqueoussolution of metal hydroxide or an aqueous solution containing metalhydroxide fine particles to the solidifying agent in the first or secondaspect, the solidifying agent in the first or second aspect coats orsoaks in the fibrous treatment objects to be treated.

According to an eighth aspect of the present invention, in the method offixing treatment for the fibrous treatment objects to be treated in oneof the fourth to seventh aspects, after or while adding a sizing agentto the solidifying agent in the first or second aspect, the solidifyingagent in the first or second aspect coats or soaks in the fibroustreatment objects to be treated.

According to a ninth aspect of the present invention, in the method offixing treatment for the fibrous treatment objects to be treated in oneof the fourth to eighth aspects, after the solidifying agent in thefirst or second aspect coats or soaks in the fibrous treatment objectsto be treated, the sulfur is dried naturally or forcibly to crystallize,thereby hardening the fibrous treatment objects.

According to a tenth aspect of the present invention, in the method offixing treatment for the fibrous treatment objects to be treated in oneof the fourth to ninth aspects, the solidifying agent in the first orsecond aspect coats or soaks in the fibrous treatment objects to betreated, so that the solidifying agent reaches a surface of a metalstructure to which the fibrous treatment objects are adhered.

PREFERRED EMBODIMENTS OF THE INVENTION

According to the present invention, a solidifying agent for fibroustreatment objects to be treated mainly contains an aqueous sulfidesolution, in which one or a mixture of Group 1 or Group 2 metals orother alkali metal substances is ionically bonded with sulfur.

Further, the solidifying agent for fibrous treatment objects to betreated may contain an aqueous solution of polysulfide of one or amixture of Group 1 or Group 2 metals or other alkali metal substances.

Further, the solidifying agent for fibrous treatment objects to betreated may contain an aqueous solution of metal hydroxide or an aqueoussolution containing fine particles of metal hydroxide.

Here, the fibrous treatment objects to be treated include naturalmineral fibers, which are represented by asbestos, or metal fibers.

The Group 1 metal includes one of lithium (Li), sodium (Na), potassium(K), rubidium (Rb), cesium (Cs), and francium (Fr). The Group 2 metalincludes one of beryllium (Be), magnesium (Mg), calcium (Ca), strontium(Sr), barium (Ba), and radium (Ra). The other alkali metal substanceincludes a single substance or a substance that can form alkali metal byaddition of water or by heating, such as slaked lime and quicklime and amixture of them. The aqueous sulfide solution includes an aqueoussolution of lithium sulfide (Li₂S), sodium sulfide (Na₂S), potassiumsulfide (K₂S), rubidium sulfide (Rb₂S), cesium sulfide (Cs₂S), franciumsulfide (Fr₂S), beryllium sulfide (BeS), magnesium sulfide (MgS),calcium sulfide (CaS), strontium sulfide (SrS), barium sulfide (BaS),and radium sulfide (RaS). The aqueous solution of polysulfide includesan aqueous solution of lithium sulfide (Li₂S_(x)), sodium sulfide(Na₂S_(x)), potassium sulfide (K₂S_(x)), rubidium sulfide (Rb₂S_(x)),cesium sulfide (Cs₂S_(x)) francium sulfide (Fr₂S_(x)), beryllium sulfide(BeS_(x)), magnesium sulfide (MgS_(x)), calcium sulfide (CaS_(x)),strontium sulfide (SrS_(x)), barium sulfide (BaS_(x)), and radiumsulfide (RaS_(x)), where x=6 to 12. The metal hydroxide includes lithiumhydroxide (Li₂OH), sodium hydroxide (Na₂OH), potassium hydroxide (K₂OH),rubidium hydroxide (Rb₂OH), cesium hydroxide (Cs₂OH), francium hydroxide(Fr₂OH), beryllium hydroxide (BeOH), magnesium hydroxide (MgOH), calciumhydroxide (CaOH), strontium hydroxide (SrOH), barium hydroxide (BaOH),and radium hydroxide (RaOH).

The aqueous sulfide solution, in which one or a mixture of the Group 1or Group 2 metals or other alkali metal substances is ionically bondedwith sulfur; the aqueous solution of polysulfide of one or a mixture ofthe Group 1 or Group 2 metals or other alkali metal substances; and theaqueous solution of metal hydroxide or the aqueous solution containingfine particles of metal hydroxide can be prepared by well-known chemicalreactions.

As a method of stably and safely producing polysulfide (Sx, where x=6 to12), there is a method of producing by reacting one or a mixture ofpotassium hydroxide, magnesium hydroxide, calcium hydroxide, and sodiumhydroxide with sulfur in an airtight container under high pressure at 98to 345° C. without exhausting steam, while mixing by stirring.

For example, when calcium hydroxide and sulfur are used, the polysulfidecan be produced through mixing slaked lime, sulfur, and water. At thistime, the following reaction occurs:

Ca(OH)₂→Ca⁺⁺+2OH⁻⁻

Ca⁺⁺+S→CaS

CaS reacts through the following reaction:

2CaS+4OH⁻⁻→H₂S+Ca(OH)₂+S+Ca+O₂

In a conventional production method, part of hydrogen sulfide and oxygenis exhausted to air as steam. In the present invention, it is designedto perform the reaction in an airtight container without exhaustingsteam.

Therefore, the above reaction accurately progresses, and the followingreaction occurs:

H₂S+Ca(OH)₂+S+Ca→Ca(HS)₂+Ca(OH)₂

CaS reacts through the following reaction:

2CaS+2H₂O→Ca(HS)₂+Ca(OH)₂

Further, CaS reacts through the following reaction:

CaS+(x−1)S→CaS_(x)

Accordingly, CaS_(x) (x=6) is stably produced.

The above process is not limited to when calcium hydroxide is used. Itis possible to stably produce a treating agent containing S_(x) (x=6)when one or a mixture of potassium hydroxide, magnesium hydroxide,calcium hydroxide, and sodium hydroxide is used.

Especially, when one of or a mixture of potassium hydroxide, magnesiumhydroxide, calcium hydroxide, and sodium hydroxide is mixed and reactedwith sulfur, while stirring so as to pulverize and peel off potassium,magnesium, calcium, or sodium, which is adhered on sulfur particlesurfaces, the treating agent mainly containing the polysulfide (S_(x),where x=6)) can be more stably produced.

Further, when the reaction is performed at a dissolving temperature ofsulfur or higher temperature, the treating agent mainly containing thepolysulfide (S_(x), where x=8) can be stably produced.

Further, when a specified amount of one or a mixture of potassiumhydroxide, magnesium hydroxide, calcium hydroxide, and sodium hydroxideis consecutively mixed into a mixed solution of sulfur and hot water,the treating agent mainly containing the polysulfide (S_(x), where x=8to 10) can be stably produced.

Further, when slaked lime is mixed into a mixed solution of sulfur, hotwater, and one of or a mixture of potassium hydroxide, magnesiumhydroxide, calcium hydroxide, and sodium hydroxide under a lowtemperature (−20° C. to 0° C.), the treating agent containing asolidifying agent in a milky state, which can harden untreatedsubstances and mainly contains the polysulfide (S_(x), where x=6 to 12),can be stably produced.

Further, when calcium is mixed into a mixed solution of sulfur, hotwater, and one of or a mixture of potassium hydroxide, magnesiumhydroxide, calcium hydroxide, and sodium hydroxide under a lowtemperature (−30° C. to −25° C.), the treating agent mainly containingthe polysulfide (S_(x), where x=8) can be stably produced.

Further, sulfur is pulverized into 100 μm or smaller size (preferably 50μm or smaller) in advance. Then, one of or a mixture of potassiumhydroxide, magnesium hydroxide, calcium hydroxide, and sodium hydroxideis mixed with sulfur in a powder state or silt state. Accordingly, thetreating agent mainly containing the polysulfide (S_(x), where x=10 to12) can be stably produced.

In the embodiment, the solidifying agent may be produced from alkalineash, which is waste, as a raw material. For example, fly ash (which isproduced from mixing and burning 50% Musselburgh and 50% Drayton coals,and has alkalinity of pH 13.5) is used as the alkaline ash. The fly ash,sulfur, and water are mixed in a reaction vessel at a ratio of 20 partsby weight of the fly ash, 20 parts by weight of sulfur, and 100 parts byweight of water. In the process, 20 parts by weight of the fly ash ismixed with 100 parts by weight of water in the reaction vessel. Afterclosing an upper lid of the reaction vessel, the mixture is stirred forabout ten minutes with a mixer.

In the next step, a safety valve is set, and an exhaust pressure is setat about 10 kg/cm² as an upper reaction pressure limit. Then, a furnacecooling water discharging valve, a cooling valve, and a cooling waterinlet valve are opened to flow water.

In the next step, in order to suppress evaporation during the reaction,a pilot pressure of about 2.5 kg/cm² is applied with an air compressor.

In the next step, a burner is turned on to increase a temperature of thereaction vessel as mixing, while checking a pressure meter and athermometer. At this time, the pressure is maintained under 10 kg/cm².When the thermometer reaches 110° C., the mixture is reacted for about30 minutes while mixing.

In the next step, the burner is turned off, and the reaction vessel isplaced quietly until the pressure meter comes down. When the pressurebecomes stable, a residual pressure is completely discharged through anexhaust valve, thereby making the pressure equal to an atmosphericpressure.

In the next step, the mixer is stopped and the exhaust valve is opened.Then, the deposits and liquid are discharged and collected.

In the next step, the collected substance is cooled to obtain a chemicalsolution and a precipitate through precipitation. Accordingly, 130 partsby weight of the chemical solution and 20 parts by weight of theprecipitate are obtained.

The collected chemical solution, i.e., a yellowish green liquid,contains calcium polysulfide, and has a liquid density of 1.2 g/cc andpH of 10.

When the fly ash having pH of 13.5 from an incinerator is used as a rawmaterial, a brown liquid, which contains calcium polysulfide and has aliquid density of 1.15 g/cc and pH of 11, is obtained.

The liquid and the aqueous solution of the precipitate obtained in themethod described above can be used as the solidifying agent.

When surfaces of the fibrous treatment objects to be treated are coatedwith the solidifying agent described above or the solidifying agentsoaks in the fibrous treatment objects to be treated, the solidifyingagent penetrates inside the fibrous treatment objects and hardens thefibrous treatment objects. For example, when the solidifying agent isapplied to a ceiling of a room in which asbestos are used, aconcentration of the asbestos is reduced to 1.1 fibers/l from 132fibers/l before the application.

Especially when the fibrous treatment objects to be treated, which areadhered to a surface of a metallic structure such as a column or a beam,are coated with an enough amount of the solidifying agent or an enoughamount of the solidifying agent soaks in the fibrous treatment objectsto be treated to reach the surface of inner metallic structure, thesurface of the metal structure can be modified from metal oxide to metalsulfide, thereby obtaining anti-rusting effect to the metal structure.

In addition, after adding a surfactant to the solidifying agent, thesolidifying agent may coat the fibrous treatment objects to be treated,or the solidifying agent may soak in the fibrous treatment objects to betreated. In this case, it is possible to effectively permeate thesolidifying agent in the hardening process.

Further, after adding water to the solidifying agent to adjust aspecific gravity thereof, the solidifying agent may coat the fibroustreatment objects to be treated, or the solidifying agent may soak inthe fibrous treatment objects to be treated. In this case, it ispossible to effectively permeate the solidifying agent and adjuststrength of the solidifying agent. For example, in a case of thechemical solution containing calcium polysulfide, when asbestos areremoved after hardening, the specific gravity of the solidifying agentmay be controlled in a range of 1.05 g/cc to 1.1 g/cc in view of thepermeability rather than the strength. In a case of a normal hardeningprocess, the specific gravity of the solidifying agent may be controlledin a range of 1.1 g/cc to 1.2 g/cc. In a case of hardening asbestos thatare significantly deteriorated, the specific gravity may be controlledin a range of 1.2 g/cc to 1.35 g/cc in view of the strength.

Further, the fibrous treatment objects to be treated may be coated withthe aqueous solution of metal hydroxide or the aqueous solutioncontaining fine particles of metal hydroxide or the aqueous solution ofmetal hydroxide or the aqueous solution containing fine particles ofmetal hydroxide may soak in the fibrous treatment objects to be treated,after adding the aqueous solution to the solidifying agent. Further, theaqueous solution of metal hydroxide or the aqueous solution containingfine particles of metal hydroxide and the solidifying agent are sprayedto the fibrous treatment objects to be treated simultaneously, so thatthe aqueous solution is added to the solidifying agent and the fibroustreatment objects to be treated may be coated with or soaked in thesolidifying agent.

Further, after or while a sizing agent is added to the solidifyingagent, the solidifying agent may coat the fibrous treatment objects tobe treated, or the solidifying agent may soak in the fibrous treatmentobjects to be treated. In this case, it is possible to effectivelyadhere the solidifying agent.

Further, after the solidifying agent may coat the fibrous treatmentobjects to be treated, or the solidifying agent may soak in the fibroustreatment objects to be treated, sulfur may be crystallized throughnaturally or forcedly drying, thereby hardening the fibrous treatmentobjects to be treated.

In this case, sulfur crystals grow in a needle shape inside and on asurface of the fibrous treatment objects to be treated, therebyimproving strength.

Even when linear gaps are formed in a film of the solidifying agent,which is formed on the surface of the fibrous treatment objects to betreated, the sulfur crystals in a needle shape grow from the gaps andclose the gaps, thereby improving strength. Furthermore, paint or thelike may be top-coated to crash the crystals in a needle shape, therebycompletely sealing the gaps.

INDUSTRIAL APPLICABILITY

In the solidifying agent for the fibrous treatment objects to be treatedor the method of fixing treatment for the fibrous treatment objects tobe treated according to the present invention, it is possible to coat orsoak the fibrous treatment objects to be treated with or in thesolidifying agent for a purpose of continuous use after hardening thefibrous treatment objects to be treated. Further, it is possible to usethe solidifying agent for a purpose of peeling after hardening thefibrous treatment objects to be treated. In this case, it is possible toprevent the fibrous treatment objects to be treated from scatteringduring a process of peeling.

1. A solidifying agent for fibrous treatment objects to be treated,comprising: an aqueous sulfide solution, in which one or a mixture ofGroup 1 or Group 2 metals or other alkali metal substances is ionicallybonded with sulfur.
 2. A solidifying agent for fibrous treatment objectsto be treated, comprising: an aqueous solution of polysulfide of one ora mixture of Group 1 or Group 2 metals or other alkali metal substances.3. The solidifying agent for fibrous treatment objects to be treatedaccording to claim 1, further comprising: an aqueous solution of metalhydroxide or an aqueous solution containing fine particles of metalhydroxide.
 4. A method of fixing treatment for fibrous treatment objectsto be treated, comprising the step of: coating the fibrous treatmentobjects to be treated with the solidifying agent according to claim 1 orsoaking the solidifying agent according to claim 1 in the fibroustreatment objects to be treated, thereby hardening the fibrous treatmentobjects to be treated.
 5. The method of fixing treatment for the fibroustreatment objects to be treated according to claim 4, wherein saidsolidifying agent according to claim 1 coats or soaks in the fibroustreatment objects to be treated after adding a surfactant to thesolidifying agent according to claim
 1. 6. The method of fixingtreatment for the fibrous treatment objects to be treated according toclaim 4, wherein said solidifying agent according to claim 1 coats orsoaks in the fibrous treatment objects to be treated after adding waterto the solidifying agent to adjust a specific gravity thereof.
 7. Themethod of fixing treatment for the fibrous treatment objects to betreated according to claims 4, said solidifying agent according to claim1 coats or soaks in the fibrous treatment objects to be treated after orwhile adding an aqueous solution of metal hydroxide or an aqueoussolution containing fine particles of metal hydroxide to the solidifyingagent according to claim
 1. 8. The method of fixing treatment for thefibrous treatment objects to be treated according to claims 4, whereinsaid solidifying agent according to claim 1 coats or soaks in thefibrous treatment objects to be treated after or while adding a sizingagent to the solidifying agent according to claim
 1. 9. The method offixing treatment for the fibrous treatment objects to be treatedaccording to claims 4, wherein said sulfur is naturally or enforcedlydried to crystallize to harden the fibrous treatment objects to betreated after the solidifying agent according to claim 1 coats or soaksin the fibrous treatment objects to be treated.
 10. The method of fixingtreatment for the fibrous treatment objects to be treated according toclaims 4, wherein said solidifying agent according to claim 1 coats orsoaks in the fibrous treatment objects to be treated so that thesolidifying agent reaches a surface of a metal structure to which thefibrous treatment objects to be treated adhere.